1. Field of the Invention
Embodiments of the present invention are generally directed toward novel uses of heterodiamondoids and heterodiamondoid-containing materials in field emission devices. Specifically, the heteroatoms of the heterodiamondoids of the present embodiments are electron donating species, and the field emission device (FED) contains an electron-emitting cold cathode.
2. State of the Art
Carbon-containing materials offer a variety of potential uses in microelectronics. As an element, carbon displays a variety of different structures, some crystalline, some amorphous, and some having regions of both, but each form having a distinct and potentially useful set of properties.
A review of carbon's structure-property relationships has been presented by S. Prawer in a chapter titled “The Wonderful World of Carbon,” in Physics of Novel Materials (World Scientific, Singapore, 1999), pp. 205-234. Prawer suggests the two most important parameters that may be used to predict the properties of a carbon-containing material are, first, the ratio of sp2 to sp3 bonding in a material, and second, microstructure, including the crystallite size of the material, i.e. the size of its individual grains.
Elemental carbon has the electronic structure 1s22s22p2, where the outer shell 2s and 2p electrons have the ability to hybridize according to two different schemes. The so-called sp3 hybridization comprises four identical σ bonds arranged in a tetrahedral manner. The so-called sp2-hybridization comprises three trigonal (as well as planar) σ bonds with an unhybridized p electron occupying a π orbital in a bond oriented perpendicular to the plane of the σ bonds. At the “extremes” of crystalline morphology are diamond and graphite. In diamond, the carbon atoms are tetrahedrally bonded with sp3-hybridization. Graphite comprises planar “sheets” of sp2-hybridized atoms, where the sheets interact weakly through perpendicularly oriented π bonds. Carbon exists in other morphologies as well, including amorphous forms called “diamond-like carbon,” and the highly symmetrical spherical and rod-shaped structures called “fullerenes” and “nanotubes,” respectively.
Diamond is an exceptional material because it scores highest (or lowest, depending on one's point of view) in a number of different categories of properties. Not only is it the hardest material known, but it has the highest thermal conductivity of any material at room temperature. It displays superb optical transparency from the infrared through the ultraviolet, has the highest refractive index of any clear material, and is an excellent electrical insulator because of its very wide bandgap. It also displays high electrical breakdown strength, and very high electron and hole mobilities. If diamond as a microelectronics material has a flaw, it would be that while diamond may be effectively doped with boron to make a p-type semiconductor, efforts to implant diamond with electron-donating elements such as phosphorus, to fabricate an n-type semiconductor, have (to the inventors' knowledge) thus far been unsuccessful.
Attempts to synthesize diamond films using chemical vapor deposition (CVD) techniques date back to about the early 1980's. An outcome of these efforts was the appearance of new forms of carbon largely amorphous in nature, yet containing a high degree of sp3-hybridized bonds, and thus displaying many of the characteristics of diamond. To describe such films the term “diamond-like carbon” (DLC) was coined, although this term has no precise definition in the literature. In “The Wonderful World of Carbon,” Prawer teaches that since most diamond-like materials display a mixture of bonding types, the proportion of carbon atoms which are four-fold coordinated (or sp3-hybridized) is a measure of the “diamond-like” content of the material. Unhybridized p electrons associated with sp2-hybridization form π bonds in these materials, where the π bonded electrons are predominantly delocalized. This gives rise to the enhanced electrical conductivity of materials with sp2 bonding, such as graphite. In contrast, sp3-hybridization results in the extremely hard, electrically insulating and transparent characteristics of diamond. The hydrogen content of a diamond-like material will be directly related to the type of bonding it has. In diamond-like materials the bandgap gets larger as the hydrogen content increases, and hardness often decreases. Not surprisingly, the loss of hydrogen from a diamond-like carbon film results in an increase in electrical activity and the loss of other diamond-like properties as well.
Nonetheless, it is generally accepted that the term “diamond-like carbon” may be used to describe two different classes of amorphous carbon films, one denoted as “a:C-H,” because hydrogen acts to terminate dangling bonds on the surface of the film, and a second hydrogen-free version given the name “ta-C” because a majority of the carbon atoms are tetrahedrally coordinated with sp3-hybridization. The remaining carbons of ta-C are surface atoms that are substantially sp2-hybridized. In a:C-H, dangling bonds can relax to the sp2 (graphitic) configuration. The role hydrogen plays in a:C-H is to prevent unterminated carbon atoms from relaxing to the graphite structure. The greater the sp3 content the more “diamond-like” the material is in its properties such as thermal conductivity and electrical resistance.
In his review article, Prawer states that tetrahedral amorphous carbon (ta-C) is a random network showing short-range ordering that is limited to one or two nearest neighbors, and no long-range ordering. There may be present random carbon networks that may comprise 3, 4, 5, and 6-membered carbon rings. Typically, the maximum sp3 content of a ta-C film is about 80 to 90 percent. Those carbon atoms that are sp2 bonded tend to group into small clusters that prevent the formation of dangling bonds. The properties of ta-C depend primarily on the fraction of atoms having the sp3, or diamond-like configuration. Unlike CVD diamond, there is no hydrogen in ta-C to passivate the surface and to prevent graphite-like structures from forming. The fact that graphite regions do not appear to form is attributed to the existence of isolated sp2 bonding pairs and to compressive stresses that build up within the bulk of the material.
The microstructure of a diamond and/or diamond-like material further determines its properties, to some degree because the microstructure influences the type of bonding content. As discussed in “Microstructure and grain boundaries of ultrananocrystalline diamond films” by D. M. Gruen, in Properties, Growth and Applications of Diamond, edited by M. H. Nazaré and A. J. Neves (Inspec, London, 2001), pp. 307-312, recently efforts have been made to synthesize diamond having crystallite sizes in the “nano” range rather than the “micro” range, with the result that grain boundary chemistries may differ dramatically from those observed in the bulk. Nanocrystalline diamond films have grain sizes in the three to five nanometer range, and it has been reported that nearly 10 percent of the carbon atoms in a nanocrystalline diamond film reside in grain boundaries.
In Gruen's chapter, the nanocrystalline diamond grain boundary is reported to be a high-energy, high angle twist grain boundary, where the carbon atoms are largely π-bonded. There may also be sp2 bonded dimers, and chain segments with sp3-hybridized dangling bonds. Nanocrystalline diamond is apparently electrically conductive, and it appears that the grain boundaries are responsible for the electrical conductivity. The author states that a nanocrystalline material is essentially a new type of diamond film whose properties are largely determined by the bonding of the carbons within grain boundaries.
Another allotrope of carbon known as the fullerenes (and their counterparts carbon nanotubes) has been discussed by M. S. Dresslehaus et al. in a chapter entitled “Nanotechnology and Carbon Materials,” in Nanotechnology (Springer-Verlag, New York, 1999), pp. 285-329. Though discovered relatively recently, these materials already have a potential role in microelectronics applications. Fullerenes have an even number of carbon atoms arranged in the form of a closed hollow cage, wherein carbon-carbon bonds on the surface of the cage define a polyhedral structure. The fullerene in the greatest abundance is the C60 molecule, although C70 and C80 fullerenes are also possible. Each carbon atom in the C60 fullerene is trigonally bonded with sp2-hybridization to three other carbon atoms.
C60 fullerene is described by Dresslehaus as a “rolled up” graphine sheet forming a closed shell (where the term “graphine” means a single layer of crystalline graphite). Twenty of the 32 faces on the regular truncated icosahedron are hexagons, with the remaining 12 being pentagons. Every carbon atom in the C60 fullerene sits on an equivalent lattice site, although the three bonds emanating from each atom are not equivalent. The four valence electrons of each carbon atom are involved in covalent bonding, so that two of the three bonds on the pentagon perimeter are electron-poor single bonds, and one bond between two hexagons is an electron-rich double bond. A fullerene such as C60 is further stabilized by the Kekulé structure of alternating single and double bonds around the hexagonal face.
Dresslehaus et al. further teach that, electronically, the C60 fullerene molecule has 60 π electrons, one π electronic state for each carbon atom. Since the highest occupied molecular orbital is fully occupied and the lowest un-occupied molecular orbital is completely empty, the C60 fullerene is considered to be a semiconductor with very high resistivity. Fullerene molecules exhibit weak van der Waals cohesive interactive forces toward one another when aggregated as a solid.
The following table summarizes a few of the properties of diamond, DLC (both ta-C and a:C-H), graphite, and fullerenes:
C60PropertyDiamondta-Ca: C—HGraphiteFullereneC—C bond length (nm)  0.154 ≈0.1520.141pentagon: 0.146hexagon: 0.140Density (g/cm3)  3.51 >30.9–2.22.27 1.72Hardness (Gpa) 100>40<60softVan der WaalsThermal conductivity2000100–70010 0.4(W/mK)Bandgap (eV)  5.45 ≈30.8–4.0metallic 1.7Electrical resistivity (Ω cm) >1016 1010 102–101210−3 − 1>108Refractive Index  2.4 2–31.8–2.4——
The data in the table is compiled from p. 290 of the Dresslehaus et al. reference cited above, p. 221 of the Prawer reference cited above, p. 891 a chapter by A. Erdemir et al. in “Tribology of Diamond, Diamond-Like Carbon, and Related Films,” in Modern Tribology Handbook, Vol. Two, B. Bhushan, Ed. (CRC Press, Boca Raton, 2001), and p. 28 of “Deposition of Diamond-Like Superhard Materials,” by W. Kulisch, (Springer Verlag, New York, 1999).
A form of carbon not discussed extensively in the literature are “diamondoids.” Diamondoids are bridged-ring cycloalkanes that comprise adamantane, diamantane, triamantane, and the tetramers, pentamers, hexamers, heptamers, octamers, nonamers, decamers, etc., of adamantane (tricyclo[3.3.1.13,7] decane), adamantane having the stoichiometric formula C10H16, in which various adamantane units are face-fused to form larger structures. These adamantane units are essentially subunits of diamondoids. The compounds have a “diamondoid” topology in that their carbon atom arrangements are superimposable on a fragment of an FCC (face centered cubic) diamond lattice.
Diamondoids are highly unusual forms of carbon because while they are hydrocarbons, with molecular sizes ranging in general from about 0.2 to 20 nm (averaged in various directions), they simultaneously display the electronic properties of an ultrananocrystalline diamond. As hydrocarbons they can self-assemble into a van der Waals solid, possibly in a repeating array with each diamondoid assembling in a specific orientation. The solid results from cohesive dispersive forces between adjacent C-Hx groups, the forces more commonly seen in normal alkanes.
In diamond nanocrystallites the carbon atoms are entirely sp3-hybridized, but because of the small size of the diamondoids, only a small fraction of the carbon atoms are bonded exclusively to other carbon atoms. The majority have at least one hydrogen nearest neighbor. Thus, the majority of the carbon atoms of a diamondoid occupy surface sites (or near surface sites), giving rise to electronic states that are significantly different energetically from bulk energy states. Accordingly, diamondoids are expected to have unusual electronic properties.
To the inventors' knowledge, adamantane, substituted adamantanes, and perhaps diamantane are the only readily available diamondoids. Some diamantanes, substituted diamantanes, triamantanes, and substituted triamantanes have been studied, and only a single tetramantane has been synthesized. The remaining diamondoids are provided for the first time by the inventors, and are described in their co-pending U.S. Provisional Patent Applications Nos. 60/262,842, filed Jan. 19, 2001; 60/300,148, filed Jun. 21, 2001; 60/307,063, filed Jul. 20, 2001; 60/312,563, filed Aug. 15, 2001; 60/317,546, filed Sep. 5, 2001; 60/323,883, filed Sep. 20, 2001; 60/334,929, filed Dec. 4, 2001; and 60/334,938, filed Dec. 4, 2001, incorporated herein in their entirety by reference. Applicants further incorporate herein by reference, in their entirety, the non-provisional applications sharing these titles which were filed on Dec. 12, 2001. The diamondoids that are the subject of these co-pending applications have not been made available for study in the past, and to the inventors' knowledge they have never been used before in as an elecron-emitting cathode in a field emission device.